US10669378B2 - Poly(thioethers) for metal ion sequestration - Google Patents

Poly(thioethers) for metal ion sequestration Download PDF

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US10669378B2
US10669378B2 US16/094,844 US201716094844A US10669378B2 US 10669378 B2 US10669378 B2 US 10669378B2 US 201716094844 A US201716094844 A US 201716094844A US 10669378 B2 US10669378 B2 US 10669378B2
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alkyl
hydroxy
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alkynyl
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Agostino Pietrangelo
Anshuman Mangalum
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Rutgers State University of New Jersey
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/06—Polythioethers from cyclic thioethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/10—Polythioethers from sulfur or sulfur-containing compounds and aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G85/00—General processes for preparing compounds provided for in this subclass
    • C08G85/004—Modification of polymers by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/04—Polysulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/206—Manganese or manganese compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates

Definitions

  • the present invention provides compounds that are useful to treat water contaminated with heavy metals. Accordingly, the invention provides a polymer comprising two or more residues of formula III or a salt thereof:
  • each dash line is independently a single bond or a double bond
  • L is (C 1 -C 6 )alkylene, (C 2 -C 6 )alkenylene, (C 2 -C 6 )alkynylene or arylene, wherein one or more carbon atoms in the alkylene, alkenylene and alkynylene is optionally replaced by —O—, —NH— or —S—, and wherein the alkylene, alkenylene, alkynylene and arylene are optionally substituted by one or more groups selected from halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2
  • Q is (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl or aryl and wherein the alkyl, alkenyl, alkynyl and aryl are optionally substituted by one or more groups selected from halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(
  • R a is selected from the group consisting of hydrogen, halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(O)—OR 3 , —N(R 3 )—C(O)—R 3 and —N(R 3 )—C(O)—N(R 3 ) 2 ;
  • R b is selected from the group consisting of hydrogen, halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(O)—OR 3 , —N(R 3 )—C(O)—R 3 and —N(R 3 )—C(O)—N(R 3 ) 2 ;
  • R c is selected from the group consisting of hydrogen, halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(O)—OR 3 , —N(R 3 )—C(O)—R 3 and —N(R 3 )—C(O)—N(R 3 ) 2 ;
  • R d is selected from the group consisting of hydrogen, halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(O)—OR 3 , —N(R 3 )—C(O)—R 3 and —N(R 3 )—C(O)—N(R 3 ) 2 ;
  • each R 3 is independently hydrogen or (C 1 -C 6 )alkyl
  • n 0, 1 or 2.
  • the invention also provides processes and intermediates disclosed herein that are useful for preparing a polymer of the invention.
  • the invention also provides a method for separating a metal from a solution that comprises the metal comprising contacting the solution with a polymer of the invention under conditions whereby the metal associates with the polymer to form a polymer associated metal.
  • FIG. 2 shows schematic representation of how poly-2b can be used with a commercially available centrifuge tube equipped with a cellulose membrane to extract Pb 2+ from water.
  • FIG. 3 shows AA spectroscopy results from control experiments.
  • An aqueous solution of lead ions [Pb 2+ ] 0 , ca. 10 ppm
  • the dot labeled by arrow represents [Pb 2+ ] in the filtrate.
  • FIG. 4 shows AA spectroscopy results from poly-2b Pb 2+ -binding experiments.
  • the dot labeled by arrow represents [Pb 2+ ] in the filtrate.
  • halo is fluoro, chloro, bromo, or iodo.
  • alkyl by itself or as part of another substituent, means, unless otherwise stated, a straight or branched chain hydrocarbon radical, having the number of carbon atoms designated (i.e., C 1-6 means one to six carbons).
  • alkenyl refers to an unsaturated alkyl radical having one or more double bonds.
  • alkynyl refers to an unsaturated alkyl radical having one or more triple bonds.
  • haloalkyl or hydroxyalkyl means an alkyl that is optionally substituted with halo or hydroxyl.
  • alkoxy refers to an alkyl groups attached to the remainder of the molecule via an oxygen atom (“oxy”).
  • aryl refers to a single all carbon aromatic ring or a multiple condensed all carbon ring system wherein at least one of the rings is aromatic.
  • an aryl group has 6 to 20 carbon atoms, 6 to 14 carbon atoms, 6 to 12 carbon atoms, or 6 to 10 carbon atoms.
  • Aryl includes a phenyl radical.
  • Aryl also includes multiple condensed ring systems (e.g., ring systems comprising 2, 3 or 4 rings) having about 9 to 20 carbon atoms in which at least one ring is aromatic and wherein the other rings may be aromatic or not aromatic (i.e., cycloalkyl.
  • Such multiple condensed ring systems are optionally substituted with one or more (e.g., 1, 2 or 3) oxo groups on any carbocycle portion of the multiple condensed ring system.
  • the rings of the multiple condensed ring system can be connected to each other via fused, spiro and bridged bonds when allowed by valency requirements. It is to be understood that the point of attachment of a multiple condensed ring system, as defined above, can be at any position of the ring system including an aromatic or a carbocycle portion of the ring.
  • Non-limiting examples of aryl groups include, but are not limited to, phenyl, indenyl, indanyl, naphthyl, 1, 2, 3, 4-tetrahydronaphthyl, anthracenyl, and the like.
  • alkylene means a divalent radical derived from an alkane (including branched alkane), as exemplified by —CH 2 CH 2 CH 2 CH 2 — and —CH(CH 2 )CH 2 CH 2 —.
  • alkenylene and alkynylene refer to the unsaturated forms of “alkylene” having double or triple bonds, respectively.
  • arylene means a divalent radical derived from an arene, such as phenylene.
  • Alkylene”, “alkenylene”, “alkynylene” and “arylene” are also meant to include mono and poly-halogenated variants.
  • alkali metal means the chemical elements found in Group 1 of the periodic table, such as lithium, sodium, potassium, rubidium and cesium.
  • alkali earth metal means the chemical elements found in Group 2 of the periodic table, such as beryllium, magnesium, calcium, strontium, barium and radium.
  • Lawesson's reagent means 2,4-Bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-dithione, which is a mild and convenient thionating agent for ketones, esters, and amides that allows the preparation of thioketones, thionoesters and thioamides.
  • polymers of the invention having a chiral center may exist in and be isolated in optically active and racemic forms. Some compounds may exhibit polymorphism. It is to be understood that the present invention encompasses any racemic, optically-active, polymorphic, or stereoisomeric form, or mixtures thereof, of a compound of the invention, which possess the useful properties described herein, it being well known in the art how to prepare optically active forms (for example, by resolution of the racemic form by recrystallization techniques, by synthesis from optically-active starting materials, by chiral synthesis, or by chromatographic separation using a chiral stationary phase.
  • the atom to which the bond is attached includes all stereochemical possibilities.
  • a bond in a compound formula herein is drawn in a defined stereochemical manner (e.g. bold, bold-wedge, dashed or dashed-wedge)
  • a bond in a compound formula herein is drawn in a defined stereochemical manner (e.g. bold, bold-wedge, dashed or dashed-wedge)
  • the atom to which the stereochemical bond is attached is enriched in the relative stereoisomer depicted unless otherwise noted.
  • the compound may be at least 51% the relative stereoisomer depicted.
  • the compound may be at least 60% the relative stereoisomer depicted.
  • the compound may be at least 80% the relative stereoisomer depicted.
  • the compound may be at least 90% the relative stereoisomer depicted. In another embodiment, the compound may be at least 95 the relative stereoisomer depicted. In another embodiment, the compound may be at least 99% the relative stereoisomer depicted.
  • (C 1 -C 6 )alkyl can be methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, sec-butyl, pentyl, 3-pentyl, or hexyl;
  • (C 1 -C 6 )alkoxy can be methoxy, ethoxy, propoxy, isopropoxy, butoxy, iso-butoxy, sec-butoxy, pentoxy, 3-pentoxy, or hexyloxy;
  • (C 2 -C 6 )alkenyl can be vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl;
  • a residue of the polymer has the following formula IV:
  • X is —S—, —O— or —NH—
  • Y is —S—, —O—, —NH— or —CH 2 —;
  • R 1 is selected from the group consisting of hydrogen, halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(O)—OR 3 , —N(R 3 )—C(O)—R 3 and —N(R 3 )—C(O)—N(R 3 ) 2 ; and
  • R 2 is selected from the group consisting of hydrogen, halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(O)—OR 3 , —N(R 3 )—C(O)—R 3 and —N(R 3 )—C(O)—N(R 3 ) 2 .
  • a residue of the polymer has the following formula V:
  • R 1 is hydrogen or (C 1 -C 6 )alkyl.
  • R 1 is hydrogen or methyl.
  • R 2 is hydrogen or (C 1 -C 6 )alkyl.
  • R 2 is hydrogen or methyl.
  • each dash line is a double bond.
  • R a is hydrogen
  • R b is hydrogen
  • R c is hydrogen
  • R d is hydrogen
  • each residue of the polymer is independently selected from the group consisting of:
  • each residue of the polymer is independently selected from the group consisting of:
  • one or more residues of the polymer are
  • the polymer of the invention further comprises a residue that is copolymerized from a monomer selected from the group consisting of:
  • An intermediate useful for preparing a polymer comprising two or more residues of formula III or a salt thereof is a polymer comprising a residue of the following formula I:
  • L is (C 1 -C 6 )alkylene, (C 2 -C 6 )alkenylene, (C 2 -C 6 )alkynylene or arylene, wherein one or more carbon atoms (e.g. 1, 2, or 3) in the alkylene, alkenylene and alkynylene is optionally replaced by —O—, —NH— or —S—, and wherein the alkylene, alkenylene, alkynylene and arylene are optionally substituted by one or more groups selected from halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(
  • Q is (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl or aryl and wherein the alkyl, alkenyl, alkynyl and aryl are optionally substituted by one or more groups selected from halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(
  • R a is selected from the group consisting of hydrogen, halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(O)—OR 3 , —N(R 3 )—C(O)—R 3 and —N(R 3 )—C(O)—N(R 3 ) 2 ;
  • R b is selected from the group consisting of hydrogen, halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(O)—OR 3 , —N(R 3 )—C(O)—R 3 and —N(R 3 )—C(O)—N(R 3 ) 2 ;
  • R c is selected from the group consisting of hydrogen, halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(O)—OR 3 , —N(R 3 )—C(O)—R 3 and —N(R 3 )—C(O)—N(R 3 ) 2 ;
  • R d is selected from the group consisting of hydrogen, halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(O)—OR 3 , —N(R 3 )—C(O)—R 3 and —N(R 3 )—C(O)—N(R 3 ) 2 ;
  • R 3 is independently hydrogen or (C 1 -C 6 )alkyl
  • n 0, 1 or 2.
  • the invention provides a method to prepare a polymer comprising a residue of formula I or a salt thereof, comprising converting a corresponding polymer comprising a residue of formula Ia:
  • L is (C 1 -C 6 )alkylene, (C 2 -C 6 )alkenylene, (C 2 -C 6 )alkynylene or arylene, wherein one or more carbon atoms in the alkylene, alkenylene and alkynylene is optionally replaced by —O—, —NH— or —S—, and wherein the alkylene, alkenylene, alkynylene and arylene are optionally substituted by one or more groups selected from halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2
  • Q is (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl or aryl and wherein the alkyl, alkenyl, alkynyl and aryl are optionally substituted by one or more groups selected from halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(
  • Z is —O—R 3a , —S—R 3a or —N(R 3a ) 2
  • R a is selected from the group consisting of hydrogen, halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(O)—OR 3 , —N(R 3 )—C(O)—R 3 and —N(R 3 )—C(O)—N(R 3 ) 2 ;
  • R b is selected from the group consisting of hydrogen, halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(O)—OR 3 , —N(R 3 )—C(O)—R 3 and —N(R 3 )—C(O)—N(R 3 ) 2 ;
  • R c is selected from the group consisting of hydrogen, halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(O)—OR 3 , —N(R 3 )—C(O)—R 3 and —N(R 3 )—C(O)—N(R 3 ) 2 ;
  • R d is selected from the group consisting of hydrogen, halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(O)—OR 3 , —N(R 3 )—C(O)—R 3 and —N(R 3 )—C(O)—N(R 3 ) 2 ;
  • each R 3 is independently hydrogen or (C 1 -C 6 )alkyl
  • each R 3a is independently (C 1 -C 6 )alkyl
  • n 0, 1 or 2.
  • the polymer comprising a residue of formula I is a salt with an alkali metal or an alkali earth metal.
  • the method comprises saponifying the polymer comprising a residue of formula Ia by using MOH or M(OH) 2 to provide a corresponding polymer comprising a residue of formula Ig:
  • M is an alkali metal or an alkali earth metal.
  • the method further comprises preparing the polymer comprising a residue of formula Ia by converting a corresponding compound of formula Ib:
  • the compound of formula Ib is treated with a transition metal catalyst to provide the corresponding polymer comprising a residue of formula Ia.
  • the transition metal catalyst is 1 st , 2 nd or 3 rd Generation of Grubbs' catalyst.
  • the ratio of compound of formula Ib to Grubbs' catalyst is about 100-800 to 1.
  • the method further comprises preparing the compound of formula Ib by contacting a corresponding compound of formula Ic and a corresponding compound of formula Id:
  • a mixture of the compound of formula Ic and the compound of formula Id is heated to provide the corresponding compound of formula Ib.
  • the method further comprises separating the corresponding product of formula Ib by crystallization.
  • the method further preparing the compound of formula Ic by converting a corresponding compound of formula Ie:
  • the compound of formula Ie is treated with P 4 S 10 /hexamethyldisiloxane (HMDO) or Lawesson's reagent to provide the corresponding compound of formula Ic.
  • HMDO hexamethyldisiloxane
  • Lawesson's reagent to provide the corresponding compound of formula Ic.
  • the method further comprises converting the polymer comprising a residue of formula I or a salt thereof to a corresponding polymer comprising a residue of formula III:
  • each dash line is independently a single bond or a double bond; provided that at least one dash line is a single bond.
  • Another intermediate useful for preparing the polymer comprising two or more residues of formula IV or a salt thereof is a polymer comprising a residue of the following formula II:
  • X is —S—, —O— or —NH—
  • Y is —S—, —O—, —NH— or —CH 2 —;
  • R 1 is selected from the group consisting of hydrogen, halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(O)—OR 3 , —N(R 3 )—C(O)—R 3 and —N(R 3 )—C(O)—N(R 3 ) 2 ;
  • R 2 is selected from the group consisting of hydrogen, halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(O)—OR 3 , —N(R 3 )—C(O)—R 3 and —N(R 3 )—C(O)—N(R 3 ) 2 ;
  • R a is selected from the group consisting of hydrogen, halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(O)—OR 3 , —N(R 3 )—C(O)—R 3 and —N(R 3 )—C(O)—N(R 3 ) 2 ;
  • R b is selected from the group consisting of hydrogen, halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(O)—OR 3 , —N(R 3 )—C(O)—R 3 and —N(R 3 )—C(O)—N(R 3 ) 2 ;
  • R c is selected from the group consisting of hydrogen, halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(O)—OR 3 , —N(R 3 )—C(O)—R 3 and —N(R 3 )—C(O)—N(R 3 ) 2 ;
  • R d is selected from the group consisting of hydrogen, halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(O)—OR 3 , —N(R 3 )—C(O)—R 3 and —N(R 3 )—C(O)—N(R 3 ) 2 ;
  • R 3 is independently hydrogen or (C 1 -C 6 )alkyl
  • n 0, 1 or 2.
  • the invention provides a method to prepare a polymer comprising a residue of formula II or a salt thereof, comprising converting a corresponding polymer comprising a residue of formula IIa:
  • X is —S—, —O— or —NH—
  • Y is —S—, —O—, —NH— or —CH 2 —;
  • R 1 is selected from the group consisting of hydrogen, halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(O)—OR 3 , —N(R 3 )—C(O)—R 3 and —N(R 3 )—C(O)—N(R 3 ) 2 ;
  • R 2 is selected from the group consisting of hydrogen, halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(O)—OR 3 , —N(R 3 )—C(O)—R 3 and —N(R 3 )—C(O)—N(R 3 ) 2 ;
  • R a is selected from the group consisting of hydrogen, halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(O)—OR 3 , —N(R 3 )—C(O)—R 3 and —N(R 3 )—C(O)—N(R 3 ) 2 ;
  • R b is selected from the group consisting of hydrogen, halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(O)—OR 3 , —N(R 3 )—C(O)—R 3 and —N(R 3 )—C(O)—N(R 3 ) 2 ;
  • R c is selected from the group consisting of hydrogen, halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(O)—OR 3 , —N(R 3 )—C(O)—R 3 and —N(R 3 )—C(O)—N(R 3 ) 2 ;
  • R d is selected from the group consisting of hydrogen, halo, hydroxy, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )haloalkyl, (C 1 -C 6 )alkoxy, hydroxy(C 1 -C 6 )alkyl, —NO 2 , —N(R 3 ) 2 , —CN, —C(O)—N(R 3 ) 2 , —O—R 3 , —S—R 3 , —O—C(O)—R 3 , —C(O)—R 3 , —C(O)—OR 3 , —N(R 3 )—C(O)—R 3 and —N(R 3 )—C(O)—N(R 3 ) 2 ;
  • R 3 is independently hydrogen or (C 1 -C 6 )alkyl
  • n 0, 1 or 2.
  • the polymer comprising a residue of formula II is a salt with an alkali metal or an alkali earth metal.
  • the method comprises saponifying the polymer comprising a residue of formula IIa by using MOH or M(OH) 2 to provide a corresponding polymer comprising a residue of formula IIg:
  • M is an alkali metal or an alkali earth metal.
  • the compound of formula IIb is treated with a transition metal catalyst to provide the corresponding compound of formula IIa.
  • the transition metal catalyst is 1 st , 2 nd or 3 rd Generation of Grubbs' catalyst.
  • the ratio of compound of formula IIb to Grubbs' catalyst is about 100-800 to 1.
  • a mixture of the compound of formula IIc and the compound of formula IId is heated to provide the corresponding compound of formula IIb.
  • the method further comprises separating the corresponding product of formula IIb by crystallization.
  • the method further comprises preparing the compound of formula IIc by converting a corresponding compound of formula IIe:
  • the compound of formula IIe is treated with P 4 S 10 /hexamethyldisiloxane (HMDO) or Lawesson's reagent to provide the corresponding compound of formula IIc.
  • HMDO hexamethyldisiloxane
  • Lawesson's reagent to provide the corresponding compound of formula IIc.
  • the invention also provides a method of separating a metal from a solution that comprises the metal comprising contacting the solution with a polymer under conditions whereby the metal associates with the polymer to form a polymer associated metal.
  • the polymer associates with the metal by chelation.
  • the polymer is a part of a membrane, coated on the surface of a bead or is form into a bead.
  • the membrane is part of a spiral wound module or present on the surface of porous hollow fibers.
  • the metal is lead, mercury, cadmium, chromium, arsenic, gold, manganese, selenium, silver, thallium or silver.
  • the method further comprises separating the polymer associated with the metal from the solution.
  • the method further comprises separating the polymer associated with the metal from the solution by filtration.
  • the method further comprises releasing the metal from the polymer.
  • silica column Silica column
  • Thia-Diels-Alder adduct 2 (20 mg, 0.0884 mmol) was added to 2 mL aq. NaOH solution (4 mg, 0.0972 mmol, 1.1 equiv) and stirred overnight at room temperature where it eventually dissolved. The solution was then filtered through a 0.2 ⁇ m syringe filter and the solvent removed to afford a white solid.
  • Compound 5 can be used with a commercially available centrifuge tube equipped with a cellulose membrane to extract Pb 2+ from water.
  • [Pb 2+ ] 0 100 ppm, indicating that the LPR system can be optimized to enhance performance.
  • the Pb 2+ binding capacity was determined to be 2481.9 ⁇ 158.4 and 2084.6 ⁇ 255.5 mg (Pb 2+ )/g (5) respectively, indicating that the Langmuir adsorption model that predicts a plateau may not be applicable due to the homogenous nature of the binding process (Madadrang, C. J., et al., ACS Appl. Mater. Interfaces 2012, 4, 1186-1193).

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Abstract

The invention provides a polymer comprising two or more residues of formula III or IV or salts thereof: wherein dash line, X, Y, Q, L, M, n, R1, R2, Ra, Rb, Rc and Rd have any of the values defined in the specification, as well as synthetic intermediates and synthetic methods useful for preparing the compounds. The polymer is useful to treat contaminated water by chelating metal.
Figure US10669378-20200602-C00001

Description

CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority to U.S. Provisional Application No. 62/326,414, filed Apr. 22, 2016. The entire content of the application referenced above is hereby incorporated by reference herein.
BACKGROUND OF THE INVENTION
Polychelatogens (Spivakov, B. Y., et al., Nature 1985, 315, 313-315; Geckeler, K. E., et al., Angew. Makromol. Chem. 1987, 155, 151-161; and Tülü, M., et al., Appl. Polym. Sci. 2008, 109, 2808-2814) and their heterogeneous (i.e. water-insoluble) alternatives (Alexandratos, S. D., et al., New. J. Chem. 2015, 39, 5366-5373; Alexandratos, S. D., et al., Macromolecules 2001, 34, 206-210; Bell, C. A., et al., Adv. Mater. 2006, 18, 582-586; Rivas, B. L., et al., Inorg. Chem. Commun. 2007, 10, 151-154; Ramirez, E., et al., J. Hazard. Mater. 2011, 192, 432-439; and Tomida, T., et al., Ind. Eng. Chem. Res. 2001, 40, 3557-3562) form a broad set of polymer-based reagents that are designed to sequester heavy metal contaminants in water resources that pose a risk to human health (Järup, L. Br. Med. Bull. 2003, 68, 167-182). In light of ongoing efforts to improve water quality in parts of the world where potable water is scarce (World Health Organization. Guidelines for Drinking-water Quality, 4th ed.; Gutenberg, Malta, 2011), there is a need for novel metal sequestration polymers (Elimelech, M., et al., A. Science 2011, 712-717; Shannon, M. A., et al., Nature 2008, 452, 301-310; and Hartono, M. R., et al., Water Air Soil Pollut. 2015, 226, 1-11) that are chemically flexible for performance optimization in both the solid and/or solution state.
SUMMARY OF THE INVENTION
In one aspect, the present invention provides compounds that are useful to treat water contaminated with heavy metals. Accordingly, the invention provides a polymer comprising two or more residues of formula III or a salt thereof:
Figure US10669378-20200602-C00002
wherein:
each dash line is independently a single bond or a double bond;
L is (C1-C6)alkylene, (C2-C6)alkenylene, (C2-C6)alkynylene or arylene, wherein one or more carbon atoms in the alkylene, alkenylene and alkynylene is optionally replaced by —O—, —NH— or —S—, and wherein the alkylene, alkenylene, alkynylene and arylene are optionally substituted by one or more groups selected from halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 or —N(R3)—C(O)—N(R3)2;
Q is (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl or aryl and wherein the alkyl, alkenyl, alkynyl and aryl are optionally substituted by one or more groups selected from halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 or —N(R3)—C(O)—N(R3)2;
Ra is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
Rb is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
Rc is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
Rd is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
each R3 is independently hydrogen or (C1-C6)alkyl; and
n is 0, 1 or 2.
The invention also provides processes and intermediates disclosed herein that are useful for preparing a polymer of the invention.
The invention also provides a method for separating a metal from a solution that comprises the metal comprising contacting the solution with a polymer of the invention under conditions whereby the metal associates with the polymer to form a polymer associated metal.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 shows retention (%) of Pb2+ as a function of [Pb2+]0. Data is reported as a mean with standard deviation (n=3). [5]=0.033 mg/mL, pH=ca. 6.
FIG. 2 shows schematic representation of how poly-2b can be used with a commercially available centrifuge tube equipped with a cellulose membrane to extract Pb2+ from water.
FIG. 3 shows AA spectroscopy results from control experiments. An aqueous solution of lead ions ([Pb2+]0, ca. 10 ppm) was passed through the cellulose filter. The dot labeled by arrow represents [Pb2+] in the filtrate. Experiments performed in triplicate. Data suggests that the cellulose membrane does NOT participate in lead extraction to a significant extent.
FIG. 4 shows AA spectroscopy results from poly-2b Pb2+-binding experiments. An aqueous solution of lead ions ([Pb2+]0, ca. 10 ppm) and poly-2b ([poly-2b]=0.67 mg/mL) was passed through the cellulose filter. The dot labeled by arrow represents [Pb2+] in the filtrate. Experiments performed in triplicate. Data suggests that there is no detectable lead (according to the lower detection limit of our AA spectrometer) in the filtrate.
FIG. 5 shows retention profile plotted against filtration factor Z where Z=VfV0 −1 (Vf=volume of filtrate and V0=volume of cell. Data suggests that poly-2b holds onto Pb2+ even after several washes with pure deionized water.
 DETAILED DESCRIPTION
The following definitions are used, unless otherwise described: halo is fluoro, chloro, bromo, or iodo.
The term “alkyl”, by itself or as part of another substituent, means, unless otherwise stated, a straight or branched chain hydrocarbon radical, having the number of carbon atoms designated (i.e., C1-6 means one to six carbons). The term “alkenyl” refers to an unsaturated alkyl radical having one or more double bonds. Similarly, the term “alkynyl” refers to an unsaturated alkyl radical having one or more triple bonds. The term “haloalkyl” or hydroxyalkyl” means an alkyl that is optionally substituted with halo or hydroxyl. The term “alkoxy” refers to an alkyl groups attached to the remainder of the molecule via an oxygen atom (“oxy”).
The term “aryl” as used herein refers to a single all carbon aromatic ring or a multiple condensed all carbon ring system wherein at least one of the rings is aromatic. For example, in certain embodiments, an aryl group has 6 to 20 carbon atoms, 6 to 14 carbon atoms, 6 to 12 carbon atoms, or 6 to 10 carbon atoms. Aryl includes a phenyl radical. Aryl also includes multiple condensed ring systems (e.g., ring systems comprising 2, 3 or 4 rings) having about 9 to 20 carbon atoms in which at least one ring is aromatic and wherein the other rings may be aromatic or not aromatic (i.e., cycloalkyl. Such multiple condensed ring systems are optionally substituted with one or more (e.g., 1, 2 or 3) oxo groups on any carbocycle portion of the multiple condensed ring system. The rings of the multiple condensed ring system can be connected to each other via fused, spiro and bridged bonds when allowed by valency requirements. It is to be understood that the point of attachment of a multiple condensed ring system, as defined above, can be at any position of the ring system including an aromatic or a carbocycle portion of the ring. Non-limiting examples of aryl groups include, but are not limited to, phenyl, indenyl, indanyl, naphthyl, 1, 2, 3, 4-tetrahydronaphthyl, anthracenyl, and the like.
The term “alkylene” means a divalent radical derived from an alkane (including branched alkane), as exemplified by —CH2CH2CH2CH2— and —CH(CH2)CH2CH2—. “Alkenylene” and “alkynylene” refer to the unsaturated forms of “alkylene” having double or triple bonds, respectively. The term “arylene” means a divalent radical derived from an arene, such as phenylene. “Alkylene”, “alkenylene”, “alkynylene” and “arylene” are also meant to include mono and poly-halogenated variants.
The term “alkali metal” means the chemical elements found in Group 1 of the periodic table, such as lithium, sodium, potassium, rubidium and cesium. The term “alkali earth metal” means the chemical elements found in Group 2 of the periodic table, such as beryllium, magnesium, calcium, strontium, barium and radium.
The term “Lawesson's reagent” means 2,4-Bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-dithione, which is a mild and convenient thionating agent for ketones, esters, and amides that allows the preparation of thioketones, thionoesters and thioamides.
It will be appreciated by those skilled in the art that polymers of the invention having a chiral center may exist in and be isolated in optically active and racemic forms. Some compounds may exhibit polymorphism. It is to be understood that the present invention encompasses any racemic, optically-active, polymorphic, or stereoisomeric form, or mixtures thereof, of a compound of the invention, which possess the useful properties described herein, it being well known in the art how to prepare optically active forms (for example, by resolution of the racemic form by recrystallization techniques, by synthesis from optically-active starting materials, by chiral synthesis, or by chromatographic separation using a chiral stationary phase.
When a bond in a compound formula herein is drawn in a non-stereochemical manner (e.g. flat), the atom to which the bond is attached includes all stereochemical possibilities. When a bond in a compound formula herein is drawn in a defined stereochemical manner (e.g. bold, bold-wedge, dashed or dashed-wedge), it is to be understood that the atom to which the stereochemical bond is attached is enriched in the relative stereoisomer depicted unless otherwise noted. In one embodiment, the compound may be at least 51% the relative stereoisomer depicted. In another embodiment, the compound may be at least 60% the relative stereoisomer depicted. In another embodiment, the compound may be at least 80% the relative stereoisomer depicted. In another embodiment, the compound may be at least 90% the relative stereoisomer depicted. In another embodiment, the compound may be at least 95 the relative stereoisomer depicted. In another embodiment, the compound may be at least 99% the relative stereoisomer depicted.
Specific values listed below for radicals, substituents, and ranges, are for illustration only; they do not exclude other defined values or other values within defined ranges for the radicals and substituents
Specifically, (C1-C6)alkyl can be methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, sec-butyl, pentyl, 3-pentyl, or hexyl; (C1-C6)alkoxy can be methoxy, ethoxy, propoxy, isopropoxy, butoxy, iso-butoxy, sec-butoxy, pentoxy, 3-pentoxy, or hexyloxy; (C2-C6)alkenyl can be vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl; (C2-C6)alkynyl can be ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, or 5-hexynyl; (C1-C6)haloalkyl can be iodomethyl, bromomethyl, chloromethyl, fluoromethyl, trifluoromethyl, 2-chloroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, or pentafluoroethyl; hydroxy(C1-C6)alkyl can be hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxybutyl, 4-hydroxybutyl, 1-hydroxypentyl, 5-hydroxypentyl, 1-hydroxyhexyl, or 6-hydroxyhexyl; and aryl can be phenyl, indenyl, or naphthyl.
It is understood that when n is 0, the residue of formula III has the following formula IIIa:
Figure US10669378-20200602-C00003
or a salt thereof.
It is understood that when n is 1, the residue of formula III has the following formula IIIb:
Figure US10669378-20200602-C00004
or a salt thereof.
It is understood that when n is 2, the residue of formula III has the following formula IIIc:
Figure US10669378-20200602-C00005
or a salt thereof.
In one embodiment, a residue of the polymer has the following formula IV:
Figure US10669378-20200602-C00006
or a salt thereof, wherein:
X is —S—, —O— or —NH—;
Y is —S—, —O—, —NH— or —CH2—;
R1 is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2; and
R2 is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2.
In one embodiment, a residue of the polymer has the following formula V:
Figure US10669378-20200602-C00007
or a salt thereof.
In one embodiment, R1 is hydrogen or (C1-C6)alkyl.
In one embodiment, R1 is hydrogen or methyl.
In one embodiment, R2 is hydrogen or (C1-C6)alkyl.
In one embodiment, R2 is hydrogen or methyl.
In one embodiment, each dash line is a double bond.
In one embodiment, Ra is hydrogen,
In one embodiment, Rb is hydrogen.
In one embodiment, Rc is hydrogen.
In one embodiment, Rd is hydrogen.
In one embodiment, each residue of the polymer is independently selected from the group consisting of:
Figure US10669378-20200602-C00008
and salts thereof.
In one embodiment, each residue of the polymer is independently selected from the group consisting of:
Figure US10669378-20200602-C00009
In one embodiment, one or more residues of the polymer are
Figure US10669378-20200602-C00010
In one embodiment, the polymer of the invention further comprises a residue that is copolymerized from a monomer selected from the group consisting of:
Figure US10669378-20200602-C00011
Processes for preparing a polymer comprising a residue of formula III are provided as further embodiments of the invention and are illustrated by the following procedures in which the meanings of the generic radicals are as given above unless otherwise qualified.
An intermediate useful for preparing a polymer comprising two or more residues of formula III or a salt thereof, is a polymer comprising a residue of the following formula I:
Figure US10669378-20200602-C00012
wherein:
L is (C1-C6)alkylene, (C2-C6)alkenylene, (C2-C6)alkynylene or arylene, wherein one or more carbon atoms (e.g. 1, 2, or 3) in the alkylene, alkenylene and alkynylene is optionally replaced by —O—, —NH— or —S—, and wherein the alkylene, alkenylene, alkynylene and arylene are optionally substituted by one or more groups selected from halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—R3, —N(R3)—C(O)—R3 or —N(R3)—C(O)—N(R3)2;
Q is (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl or aryl and wherein the alkyl, alkenyl, alkynyl and aryl are optionally substituted by one or more groups selected from halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 or —N(R3)—C(O)—N(R3)2;
Ra is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
Rb is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
Rc is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
Rd is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
R3 is independently hydrogen or (C1-C6)alkyl; and
n is 0, 1 or 2.
In one aspect, the invention provides a method to prepare a polymer comprising a residue of formula I or a salt thereof, comprising converting a corresponding polymer comprising a residue of formula Ia:
Figure US10669378-20200602-C00013
to provide the polymer comprising a residue of formula I or a salt thereof, wherein:
L is (C1-C6)alkylene, (C2-C6)alkenylene, (C2-C6)alkynylene or arylene, wherein one or more carbon atoms in the alkylene, alkenylene and alkynylene is optionally replaced by —O—, —NH— or —S—, and wherein the alkylene, alkenylene, alkynylene and arylene are optionally substituted by one or more groups selected from halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 or —N(R3)—C(O)—N(R3)2;
Q is (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl or aryl and wherein the alkyl, alkenyl, alkynyl and aryl are optionally substituted by one or more groups selected from halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 or —N(R3)—C(O)—N(R3)2;
Z is —O—R3a, —S—R3a or —N(R3a)2
Ra is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
Rb is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
Rc is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
Rd is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
each R3 is independently hydrogen or (C1-C6)alkyl;
each R3a is independently (C1-C6)alkyl; and
n is 0, 1 or 2.
In one embodiment, the polymer comprising a residue of formula I is a salt with an alkali metal or an alkali earth metal.
In one embodiment, the method comprises saponifying the polymer comprising a residue of formula Ia by using MOH or M(OH)2 to provide a corresponding polymer comprising a residue of formula Ig:
Figure US10669378-20200602-C00014
wherein M is an alkali metal or an alkali earth metal.
In one embodiment, the method further comprises preparing the polymer comprising a residue of formula Ia by converting a corresponding compound of formula Ib:
Figure US10669378-20200602-C00015
to provide the polymer comprising a residue of formula Ia.
In one embodiment, the compound of formula Ib is treated with a transition metal catalyst to provide the corresponding polymer comprising a residue of formula Ia.
In one embodiment, the transition metal catalyst is 1st, 2nd or 3rd Generation of Grubbs' catalyst.
In one embodiment, the ratio of compound of formula Ib to Grubbs' catalyst is about 100-800 to 1.
In one embodiment, the method further comprises preparing the compound of formula Ib by contacting a corresponding compound of formula Ic and a corresponding compound of formula Id:
Figure US10669378-20200602-C00016
to provide the compound of formula Ib.
In one embodiment, a mixture of the compound of formula Ic and the compound of formula Id is heated to provide the corresponding compound of formula Ib.
In one embodiment, the method further comprises separating the corresponding product of formula Ib by crystallization.
In one embodiment, the method further preparing the compound of formula Ic by converting a corresponding compound of formula Ie:
Figure US10669378-20200602-C00017
to provide the compound of formula Ic.
In one embodiment, the compound of formula Ie is treated with P4S10/hexamethyldisiloxane (HMDO) or Lawesson's reagent to provide the corresponding compound of formula Ic.
In another embodiment, the method further comprises converting the polymer comprising a residue of formula I or a salt thereof to a corresponding polymer comprising a residue of formula III:
Figure US10669378-20200602-C00018
or a salt thereof, wherein:
each dash line is independently a single bond or a double bond; provided that at least one dash line is a single bond.
Another intermediate useful for preparing the polymer comprising two or more residues of formula IV or a salt thereof, is a polymer comprising a residue of the following formula II:
Figure US10669378-20200602-C00019
wherein:
X is —S—, —O— or —NH—;
Y is —S—, —O—, —NH— or —CH2—;
R1 is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
R2 is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
Ra is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
Rb is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
Rc is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
Rd is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
R3 is independently hydrogen or (C1-C6)alkyl; and
n is 0, 1 or 2.
In one aspect, the invention provides a method to prepare a polymer comprising a residue of formula II or a salt thereof, comprising converting a corresponding polymer comprising a residue of formula IIa:
Figure US10669378-20200602-C00020
to provide the polymer comprising a residue of formula II or a salt thereof, wherein:
X is —S—, —O— or —NH—;
Y is —S—, —O—, —NH— or —CH2—;
R1 is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
R2 is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
Ra is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
Rb is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
Rc is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
Rd is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
R3 is independently hydrogen or (C1-C6)alkyl; and
n is 0, 1 or 2.
In one embodiment, the polymer comprising a residue of formula II is a salt with an alkali metal or an alkali earth metal.
In one embodiment, the method comprises saponifying the polymer comprising a residue of formula IIa by using MOH or M(OH)2 to provide a corresponding polymer comprising a residue of formula IIg:
Figure US10669378-20200602-C00021
wherein M is an alkali metal or an alkali earth metal.
In one embodiment the method further comprises preparing the polymer comprising a residue of formula IIa by converting a corresponding compound of formula IIb:
Figure US10669378-20200602-C00022
to provide the polymer comprising a residue of formula IIa.
In one embodiment, the compound of formula IIb is treated with a transition metal catalyst to provide the corresponding compound of formula IIa.
In one embodiment the transition metal catalyst is 1st, 2nd or 3rd Generation of Grubbs' catalyst.
In one embodiment the ratio of compound of formula IIb to Grubbs' catalyst is about 100-800 to 1.
In one embodiment the method further comprises preparing the compound of formula IIb by contacting a corresponding compound of formula IIc and a corresponding compound of formula IId:
Figure US10669378-20200602-C00023
to provide the compound of formula IIb.
In one embodiment, a mixture of the compound of formula IIc and the compound of formula IId is heated to provide the corresponding compound of formula IIb.
In one embodiment, the method further comprises separating the corresponding product of formula IIb by crystallization.
In one embodiment, the method further comprises preparing the compound of formula IIc by converting a corresponding compound of formula IIe:
Figure US10669378-20200602-C00024
to the compound of formula IIc.
In one embodiment, the compound of formula IIe is treated with P4S10/hexamethyldisiloxane (HMDO) or Lawesson's reagent to provide the corresponding compound of formula IIc.
The invention also provides a method of separating a metal from a solution that comprises the metal comprising contacting the solution with a polymer under conditions whereby the metal associates with the polymer to form a polymer associated metal.
In one embodiment, the polymer associates with the metal by chelation.
In one embodiment, the polymer is a part of a membrane, coated on the surface of a bead or is form into a bead.
In one embodiment, the membrane is part of a spiral wound module or present on the surface of porous hollow fibers.
In one embodiment, the metal is lead, mercury, cadmium, chromium, arsenic, gold, manganese, selenium, silver, thallium or silver.
In one embodiment, the method further comprises separating the polymer associated with the metal from the solution.
In one embodiment, the method further comprises separating the polymer associated with the metal from the solution by filtration.
In one embodiment, the method further comprises releasing the metal from the polymer.
The invention will now be illustrated by the following non-limiting Examples.
Example 1. Preparation of Polychelatogen 5
Figure US10669378-20200602-C00025
Step 1. Preparation of (3S,6S)-3,6-dimethyl-5-thioxo-1,4-dioxan-2-one (1)
A pressure vessel (equipped with a sidearm and stir bar) was charged with L-lactide (10.00 g, 69.40 mmol), P4S10 (7.71 g, 17.35 mmol) and hexamethyldisiloxane (18.81 g, 115.87 mmol) in ca. 70 mL of anhydrous toluene. After refluxing the contents for 24 h, the reaction was cooled to room temperature and the solvent removed under reduced pressure. The residue was taken up in DCM and passed through a silica column (Sorbtech silica gel; porosity, 60 Å; particle size, 40-60 μm; column, 4 cm diameter, 15 cm length, Rf=1.0) to remove sulfur impurities. The crude product was then passed through a second silica column (diameter, 4 cm; length, 15 cm) using a diethyl ether/hexane solvent mixture (25/75) as the eluent (Rf=0.45). After solvent removal, the yellow solid was recrystallized thrice from cold diethyl ether (ca. −20° C.) and sublimed to afford analytically pure product (2.00 g, Yield: 18%). 1H NMR (500 MHz, CDCl3): δ==5.04 (q, 3JHH=13.41, 3JHH=6.73, 1H), 4.96 (q, 3JHH=12.77, 3JHH=6.41, 1H), 1.76 (d, 3JHH=6.40, 3H), 1.73 (d, 3JHH=6.68, 3H). 13C NMR (125 MHz, CDCl3): δ 211.4, 167.5, 78.4, 75.1, 19.3, 15.5. IR: v=2996, 1759, 1441, 1370, 1350, 1323, 1303, 1259, 1226, 1147, 1080, 1063, 1035, 1010, 959, 833, 751, 727 cm−1. [α]n 23=−512.9 (c 0.59, CHCl3). Melting point: 82-83° C. Anal. Calc. for C6H8O3S: C, 44.99; H, 5.03; N, 0.0. Found: C, 45.13; H, 4.99; N, 0.00.
Step 2. Preparation of (1S,2S,3′S,4R,6′S)-3′,6′-dimethyl-3-thiaspiro[bicyclo[2.2.1]heptane-2,2′-[1,4]dioxan]-5-en-5′-one (2)
A pressure vessel (equipped with a sidearm and stir bar) was charged with 1 (1.40 g, 8.74 mmol) and freshly distilled cyclopentadiene (2.90 g, 43.72 mmol, 5 equiv) in 10 mL of anhydrous benzene and heated to 130° C. for 5 h. After cooling to room temperature, both solvent and excess cyclopentadiene were removed by reduced pressure and the residue passed through a silica gel column using a diethyl ether/hexane solvent mixture (5/95) as the eluent (Rf=0.6). Compound 2 was isolated from its mixture of stereoisomers by recrystallization from boiling hexanes (thrice) to afford a white solid (0.50 g, Yield: 18%). 1H NMR (500 MHz, CDCl3): δ=6.60 (q, 3JHH=5.71, 3JHH=2.77, 1H), 5.93 (q, 3JHH=5.62, 3JHH=3.21, 1H), 4.71 (q, 3JHH=13.99, 3JHH=7.01, 1H), 4.21 (m, 2H), 3.16 (d, 3JHH=1.72, 1H), 2.23 (d, 3JHH=9.42, 1H), 1.91 (m, 1H), 1.56 (m, 6H). 13C NMR (125 MHz, CDCl3): δ 169.8, 143.2, 129.5, 102.1, 83.3, 71.9, 54.1, 52.7, 51.6, 19.7, 18.1. IR: v=2990, 2935, 1737, 1441, 1375, 1332, 1269, 1228, 1182, 1153, 1124, 1107, 1078, 1046, 1011, 980, 970, 958, 909, 884, 812, 798, 761, 733, 691 cm−1. Melting point: 103-104° C. Anal. Calc. for C11H14O3S: C, 58.39; H, 6.24; N, 0.0. Found: C, 58.46; H, 6.11; N, 0.00. The stereochemistry of compound 2 was confirmed by X-ray crystal structure.
Step 3. Preparation of Compound 3
Thia-Diels-Alder adduct 2 (20 mg, 0.0884 mmol) was added to 2 mL aq. NaOH solution (4 mg, 0.0972 mmol, 1.1 equiv) and stirred overnight at room temperature where it eventually dissolved. The solution was then filtered through a 0.2 μm syringe filter and the solvent removed to afford a white solid. 1H NMR (500 MHz, D2O): δ=6.53 (q, 3JHH=5.56, 3JHH=2.65, 1H), 6.11 (q, 3JHH=5.50, 3JHH=3.33, 1H), 4.53 (q, 3JHH=13.89, 3JHH=6.95, 1H), 4.24 (s, 1H), 3.47 (d, 3JHH=13.11, 3JHH=6.56, 1H), 3.20 (s, 1H), 2.10 (d, 3JHH=9.63, 1H), 1.86 (d, 3JHH=9.68, 1H), 1.34 (m, 6H). 13C NMR (125 MHz, CDCl3): δ 182.5, 141.2, 132.5, 110.7, 77.0, 75.0, 55.6, 53.3, 50.7, 19.4, 18.2.
Step 4. Preparation of Compound 4
A pressure vessel (equipped with a sidearm and stir bar) was charged with 2 (100 mg, 4.4 mmol) and the appropriate amount of Grubbs 2nd generation catalyst (G2) in ca. 2 mL of anhydrous DCM. The reaction was quenched with butyl vinyl ether (10 equiv. wrt (G2)) after consumption of the monomer was complete (as determined by 1H NMR spectroscopy). Compound 4 was then precipitated upon dropwise addition of the reaction solution into cold (ca. 0° C.) methanol. After dissolving and precipitating the polymer in triplicate, the polymer was dried under vacuum for 24 h. Compound 4: ([2]0/[G2]0=100). 1H NMR (500 MHz, CDCl3): δ=7.36 (br s, 5H), 5.81−5.65 (br m, 217H), 4.70 (br s, 105H), 4.53−4.11 (br m, 221H), 3.15−2.84 (br m, 219H), 1.75 (br s, 107H), 1.55−1.42 (br m, 640H).
Step 5. Preparation of Compound 5
A solution of 4 ([2]0/[G2]0=100, 50 mg in 5 mL THF) was added to 5 mL of 1 M NaOH (aq) and stirred for 48 h at room temperature. The solution was concentrated under reduced pressure and dialyzed against a 3500 Mw cutoff in deionized water for 48 h under sink conditions. The solvent was removed by reduced pressure and the white solid dried under vacuum for 24 h (52 mg). 1H NMR (500 MHz, D2O): δ=5.77−5.66 (br m, 2H), 4.389 (br s, 1H), 4.13−4.09 (br m, 1H), 3.85 (br s, 1H), 3.34 (br, s, 1H), 3.02 (br s, 1H), 2.17 (br s, 1H), 1.92 (br s, 1H), 1.44−1.28 (br m, 5H).
Example 2. Heavy Metal Affinity Test
Compound 5 can be used with a commercially available centrifuge tube equipped with a cellulose membrane to extract Pb2+ from water. To investigate the liquid-phase polymer-based retention (LPR) of Pb2+, aqueous solutions of compound 5 (2 mL, [5]=ca. 1 mg/mL) and Pb2+ (1 mL, [Pb2+]=ca. 30 ppm) were combined ([5], ca. 0.67 mg/mL; [Pb2+]0, ca. 10 ppm) and stirred under ambient conditions for 90 min followed by centrifugation through an Amicon Ultra filter equipped with a regenerated cellulose membrane (3 kDa MWCO). Filtrate analysis by atomic absorption spectroscopy revealed no detectable Pb2+ in these solutions, even after several retentate washes (e.g., 5×3 mL) with deionized water. Indeed, filtrates from control experiments employing polymer-free solutions were found to possess Pb2+ concentrations of ca. 9.57±0.08 ppm indicating that the cellulose membrane did not play a significant role in Pb2+ binding. As anticipated from earlier results, washing the membrane with three aliquots of 1 M HCl (3 mL) afforded filtrates with [Pb2+] of 7.09, 1.63, and 0.21 ppm respectively indicating that Pb2+ can be released from the polymer upon treatment with aqueous acid.
To gain further insight into Pb2+ uptake by compound 5, Pb2+ retention (%) was measured as a function of the initial Pb2+ concentration [Pb2+]0 (FIG. 1). Indeed, a near quantitative retention of Pb2+ by the polychelatogen ([5]=ca. 0.033 mg/mL). pH=ca. 6, n=3) in solutions up to [Pb2+] ca. 50 ppm was observed, after which the Pb2+ retention drops considerably. Be that as it may, the binding capacity Pb2+ in milligrams per gram of compound 5 at [Pb2−]0=100 ppm is ca. 1925.3±148.9 mg (Pb2+)/g (5), a value that is considerably higher than many Pb2+ binding systems reported to date (Spivakov, B. Y., et al., Nature 1985, 315, 313-315; Geckeler, K. E., et al., Angew. Makromol. Chem. 1987, 155, 151-161; Tülü, M., et al., Appl. Polym. Sci. 2008, 109, 2808-2814; and Alexandratos, S. D., et al., Macromolecules 2001, 34, 206-210) Moreover, [5] concentrations could be increased to promote the near quantitative retention of Pb2+ from solutions of ca. [Pb2+]0=100 ppm, indicating that the LPR system can be optimized to enhance performance. In solutions with [Pb2+]0=150 and 200 ppm, the Pb2+ binding capacity was determined to be 2481.9±158.4 and 2084.6±255.5 mg (Pb2+)/g (5) respectively, indicating that the Langmuir adsorption model that predicts a plateau may not be applicable due to the homogenous nature of the binding process (Madadrang, C. J., et al., ACS Appl. Mater. Interfaces 2012, 4, 1186-1193).
All publications, patents, and patent documents are incorporated by reference herein, as though individually incorporated by reference. The invention has been described with reference to various specific and preferred embodiments and techniques. However, it should be understood that many variations and modifications may be made while remaining within the spirit and scope of the invention.

Claims (15)

What is claimed is:
1. A polymer comprising two or more residues of formula III or a salt thereof:
Figure US10669378-20200602-C00026
wherein:
each dash line is independently a single bond or a double bond;
L is (C1-C6)alkylene, (C2-C6)alkenylene, (C2-C6)alkynylene or arylene, wherein one or more carbon atoms in the alkylene, alkenylene and alkynylene is optionally replaced by —O—, —NH— or —S—, and wherein the alkylene, alkenylene, alkynylene and arylene are optionally substituted by one or more groups selected from halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 or —N(R3)—C(O)—N(R3)2;
Q is (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl or aryl and wherein the alkyl, alkenyl, alkynyl and aryl are optionally substituted by one or more groups selected from halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 or —N(R3)—C(O)—N(R3)2;
Ra is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
Rb is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
Rc is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
Rd is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
each R3 is independently hydrogen or (C1-C6)alkyl; and
n is 1.
2. The polymer of claim 1, wherein the residue has the following formula IIIb:
Figure US10669378-20200602-C00027
or a salt thereof.
3. The polymer of claim 1, wherein the residue has the following formula IV:
Figure US10669378-20200602-C00028
or a salt thereof, wherein:
X is —S—, —O— or —NH—;
Y is —S—, —O—, —NH— or —CH2—;
R1 is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2; and
R2 is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2.
4. The polymer of claim 3, wherein the residue has the following formula V:
Figure US10669378-20200602-C00029
or a salt thereof.
5. The polymer of claim 1, wherein each residue is independently selected from the group consisting of:
Figure US10669378-20200602-C00030
and salts thereof.
6. A method to prepare a polymer as described in claim 1, comprising, converting a corresponding polymer comprising a residue of formula Ia:
Figure US10669378-20200602-C00031
to provide the polymer comprising a residue of formula I or a salt thereof, wherein:
Z is —O—R3a, —S—R3a or —N(R3a)2; and
each R3a is independently (C1-C6)alkyl.
7. The method of claim 6, further comprising preparing the polymer comprising a residue of formula Ia by converting a corresponding compound of formula Ib:
Figure US10669378-20200602-C00032
to provide the polymer comprising a residue of formula Ia.
8. The method of claim 7, further comprising preparing the compound of formula Ib by contacting a corresponding compound of formula Ic and a corresponding compound of formula Id:
Figure US10669378-20200602-C00033
to provide the compound of formula Ib.
9. The method of claim 8, further comprising preparing the compound of formula Ic by converting a corresponding compound of formula Ie:
Figure US10669378-20200602-C00034
to provide the compound of formula Ic.
10. The method of claim 6, further comprising converting the polymer comprising a residue of formula I or a salt thereof to a corresponding polymer comprising a residue of formula III:
Figure US10669378-20200602-C00035
or a salt thereof, wherein:
each dash line is independently a single bond or a double bond; provided that at least one dash line is a single bond.
11. A method to prepare a polymer comprising a residue of formula II or a salt thereof, comprising converting a corresponding polymer comprising a residue of formula IIa:
Figure US10669378-20200602-C00036
to provide the polymer comprising a residue of formula II or a salt thereof, wherein:
X is —S—, —O— or —NH—;
Y is —S—, —O—, —NH— or —CH2—;
R1 is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
R2 is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
Ra is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
Rb is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
Rc is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
Rd is selected from the group consisting of hydrogen, halo, hydroxy, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, (C1-C6)haloalkyl, (C1-C6)alkoxy, hydroxy(C1-C6)alkyl, —NO2, —N(R3)2, —CN, —C(O)—N(R3)2, —O—R3, —S—R3, —O—C(O)—R3, —C(O)—R3, —C(O)—OR3, —N(R3)—C(O)—R3 and —N(R3)—C(O)—N(R3)2;
R3 is independently hydrogen or (C1-C6)alkyl; and
n is 1.
12. The method of claim 11, further comprising preparing the polymer comprising a residue of formula IIa by converting a corresponding compound of formula IIb:
Figure US10669378-20200602-C00037
to provide the polymer comprising a residue of formula IIa.
13. The method of claim 12, further comprising preparing the compound of formula IIb by contacting a corresponding compound of formula IIc and a corresponding compound of formula IId:
Figure US10669378-20200602-C00038
to provide the compound of formula IIb.
14. The method of claim 13, further comprising preparing the compound of formula IIc by converting a corresponding compound of formula IIe:
Figure US10669378-20200602-C00039
to provide the compound of formula IIc.
15. The method of claim 1, further comprising converting the polymer comprising a residue of formula II or a salt thereof to a polymer comprising a residue of formula IV:
Figure US10669378-20200602-C00040
or a salt thereof, wherein:
each dash line is independently a single bond or a double bond; provided that at least one dash line is a single bond.
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